CN109400476B - Preparation method of estolide - Google Patents
Preparation method of estolide Download PDFInfo
- Publication number
- CN109400476B CN109400476B CN201811483865.2A CN201811483865A CN109400476B CN 109400476 B CN109400476 B CN 109400476B CN 201811483865 A CN201811483865 A CN 201811483865A CN 109400476 B CN109400476 B CN 109400476B
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- Prior art keywords
- tower
- flash tank
- alcohol
- recovery tower
- esterification reaction
- Prior art date
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- 150000002149 estolides Chemical class 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 203
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 162
- 238000005886 esterification reaction Methods 0.000 claims abstract description 160
- 150000002148 esters Chemical class 0.000 claims abstract description 138
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 134
- 230000005496 eutectics Effects 0.000 claims abstract description 94
- 239000002904 solvent Substances 0.000 claims abstract description 94
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000011084 recovery Methods 0.000 claims description 203
- 239000012071 phase Substances 0.000 claims description 102
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 82
- 239000000203 mixture Substances 0.000 claims description 75
- 239000000047 product Substances 0.000 claims description 64
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 60
- 239000007788 liquid Substances 0.000 claims description 49
- 238000003756 stirring Methods 0.000 claims description 49
- 239000000463 material Substances 0.000 claims description 46
- 238000010992 reflux Methods 0.000 claims description 45
- 239000002994 raw material Substances 0.000 claims description 44
- 238000004064 recycling Methods 0.000 claims description 44
- 239000002253 acid Substances 0.000 claims description 43
- RXGUIWHIADMCFC-UHFFFAOYSA-N 2-Methylpropyl 2-methylpropionate Chemical compound CC(C)COC(=O)C(C)C RXGUIWHIADMCFC-UHFFFAOYSA-N 0.000 claims description 40
- 239000006227 byproduct Substances 0.000 claims description 29
- 238000005191 phase separation Methods 0.000 claims description 25
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 22
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 22
- 125000004122 cyclic group Chemical group 0.000 claims description 21
- VKFOCPKVTXIIOD-UHFFFAOYSA-N 1h-imidazol-1-ium;4-methylbenzenesulfonate Chemical compound [NH2+]1C=CN=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 VKFOCPKVTXIIOD-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 239000008346 aqueous phase Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims 1
- 239000002608 ionic liquid Substances 0.000 abstract description 91
- 239000003054 catalyst Substances 0.000 abstract description 18
- 239000000126 substance Substances 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- -1 tetrafluoroborate ion Chemical class 0.000 description 31
- 238000004821 distillation Methods 0.000 description 21
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 16
- RPRPDTXKGSIXMD-UHFFFAOYSA-N Caproic acid n-butyl ester Natural products CCCCCC(=O)OCCCC RPRPDTXKGSIXMD-UHFFFAOYSA-N 0.000 description 15
- XIRNKXNNONJFQO-UHFFFAOYSA-N ethyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCC XIRNKXNNONJFQO-UHFFFAOYSA-N 0.000 description 14
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- MMXKVMNBHPAILY-UHFFFAOYSA-N ethyl laurate Chemical compound CCCCCCCCCCCC(=O)OCC MMXKVMNBHPAILY-UHFFFAOYSA-N 0.000 description 12
- MMKRHZKQPFCLLS-UHFFFAOYSA-N ethyl myristate Chemical compound CCCCCCCCCCCCCC(=O)OCC MMKRHZKQPFCLLS-UHFFFAOYSA-N 0.000 description 12
- XVSZRAWFCDHCBP-UHFFFAOYSA-N 3-methylbutyl hexanoate Chemical compound CCCCCC(=O)OCCC(C)C XVSZRAWFCDHCBP-UHFFFAOYSA-N 0.000 description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- YRHYCMZPEVDGFQ-UHFFFAOYSA-N methyl decanoate Chemical compound CCCCCCCCCC(=O)OC YRHYCMZPEVDGFQ-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 6
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 6
- DJNTZVRUYMHBTD-UHFFFAOYSA-N Octyl octanoate Chemical compound CCCCCCCCOC(=O)CCCCCCC DJNTZVRUYMHBTD-UHFFFAOYSA-N 0.000 description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 6
- IZAJHCHUTYYTGP-UHFFFAOYSA-M cyclohexyl(trimethyl)azanium;methanesulfonate Chemical compound CS([O-])(=O)=O.C[N+](C)(C)C1CCCCC1 IZAJHCHUTYYTGP-UHFFFAOYSA-M 0.000 description 6
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 6
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 6
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 6
- ZNNXXAURXKYLQY-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCN1CN(C)C=C1 ZNNXXAURXKYLQY-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- FYWVMROQEMIMSK-UHFFFAOYSA-N butane-1-sulfonic acid;hydrogen sulfate;3-methyl-1h-imidazol-3-ium Chemical compound OS([O-])(=O)=O.C[N+]=1C=CNC=1.CCCCS(O)(=O)=O FYWVMROQEMIMSK-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229940067592 ethyl palmitate Drugs 0.000 description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 5
- ZRGWIXMPMASFPS-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;dihydrogen phosphate Chemical compound OP(O)([O-])=O.CCCC[NH+]1CN(C)C=C1 ZRGWIXMPMASFPS-UHFFFAOYSA-N 0.000 description 4
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 4
- CETWDUZRCINIHU-UHFFFAOYSA-N 2-heptanol Chemical compound CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 description 4
- 125000005916 2-methylpentyl group Chemical group 0.000 description 4
- MXLMTQWGSQIYOW-UHFFFAOYSA-N 3-methyl-2-butanol Chemical compound CC(C)C(C)O MXLMTQWGSQIYOW-UHFFFAOYSA-N 0.000 description 4
- 125000005917 3-methylpentyl group Chemical group 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- RZKSECIXORKHQS-UHFFFAOYSA-N Heptan-3-ol Chemical compound CCCCC(O)CC RZKSECIXORKHQS-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000005640 Methyl decanoate Substances 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- RGXWDWUGBIJHDO-UHFFFAOYSA-N ethyl decanoate Chemical compound CCCCCCCCCC(=O)OCC RGXWDWUGBIJHDO-UHFFFAOYSA-N 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 4
- ZOCHHNOQQHDWHG-UHFFFAOYSA-N hexan-3-ol Chemical compound CCCC(O)CC ZOCHHNOQQHDWHG-UHFFFAOYSA-N 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 4
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 4
- NMRPBPVERJPACX-UHFFFAOYSA-N octan-3-ol Chemical compound CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 4
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 4
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 3
- 235000021314 Palmitic acid Nutrition 0.000 description 3
- 229910006069 SO3H Inorganic materials 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 3
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 description 2
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- PQDJSMBWJOFMPZ-UHFFFAOYSA-N 2-methylpentane-1-sulfonic acid Chemical group CCCC(C)CS(O)(=O)=O PQDJSMBWJOFMPZ-UHFFFAOYSA-N 0.000 description 2
- FKOZPUORKCHONH-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid Chemical group CC(C)CS(O)(=O)=O FKOZPUORKCHONH-UHFFFAOYSA-N 0.000 description 2
- NMRPBPVERJPACX-QMMMGPOBSA-N 3-Octanol Natural products CCCCC[C@@H](O)CC NMRPBPVERJPACX-QMMMGPOBSA-N 0.000 description 2
- HYZYOKHLDUXUQK-UHFFFAOYSA-N 3-methylbutane-1-sulfonic acid Chemical group CC(C)CCS(O)(=O)=O HYZYOKHLDUXUQK-UHFFFAOYSA-N 0.000 description 2
- 125000003469 3-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- UPQGXHSGBPIDLB-UHFFFAOYSA-N 3-methylpentane-1-sulfonic acid Chemical group CCC(C)CCS(O)(=O)=O UPQGXHSGBPIDLB-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 229940006460 bromide ion Drugs 0.000 description 2
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical group CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical group CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000007701 flash-distillation Methods 0.000 description 2
- FYAQQULBLMNGAH-UHFFFAOYSA-N hexane-1-sulfonic acid Chemical group CCCCCCS(O)(=O)=O FYAQQULBLMNGAH-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- 229940006461 iodide ion Drugs 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- ULAHIHHGQVIRTO-UHFFFAOYSA-N methanesulfonic acid;4-methylbenzenesulfonic acid Chemical compound CS(O)(=O)=O.CC1=CC=C(S(O)(=O)=O)C=C1 ULAHIHHGQVIRTO-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- WOFPPJOZXUTRAU-UHFFFAOYSA-N octan-4-ol Chemical compound CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 2
- 229960002446 octanoic acid Drugs 0.000 description 2
- HTKPDYSCAPSXIR-UHFFFAOYSA-N octyltrimethylammonium ion Chemical compound CCCCCCCC[N+](C)(C)C HTKPDYSCAPSXIR-UHFFFAOYSA-N 0.000 description 2
- RJQRCOMHVBLQIH-UHFFFAOYSA-N pentane-1-sulfonic acid Chemical group CCCCCS(O)(=O)=O RJQRCOMHVBLQIH-UHFFFAOYSA-N 0.000 description 2
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical group CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 2
- HNDXKIMMSFCCFW-UHFFFAOYSA-N propane-2-sulphonic acid Chemical group CC(C)S(O)(=O)=O HNDXKIMMSFCCFW-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229940005605 valeric acid Drugs 0.000 description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 description 1
- NKRASMXHSQKLHA-UHFFFAOYSA-M 1-hexyl-3-methylimidazolium chloride Chemical compound [Cl-].CCCCCCN1C=C[N+](C)=C1 NKRASMXHSQKLHA-UHFFFAOYSA-M 0.000 description 1
- STCBHSHARMAIOM-UHFFFAOYSA-N 1-methyl-1h-imidazol-1-ium;chloride Chemical compound Cl.CN1C=CN=C1 STCBHSHARMAIOM-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000007309 Fischer-Speier esterification reaction Methods 0.000 description 1
- 229910016287 MxOy Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 235000019634 flavors Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- TVEOIQKGZSIMNG-UHFFFAOYSA-N hydron;1-methyl-1h-imidazol-1-ium;sulfate Chemical compound OS([O-])(=O)=O.C[NH+]1C=CN=C1 TVEOIQKGZSIMNG-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The present invention relates to the field of organic synthesis. The invention provides a preparation method of estolide, which comprises the following steps: carrying out esterification reaction on carboxylic acid and alcohol under a catalyst, and standing and layering reaction liquid to obtain a long-chain ester phase and a water phase; the catalyst comprises an ionic liquid or a eutectic solvent; purifying the long-chain ester phase, and separating to obtain high-purity long-chain ester; and after the water in the water phase is removed, the residual substances are still introduced into the esterification reaction system for reaction. The yield and the purity of the estolide prepared by the method are high, and the results of the examples show that the yield of the estolide provided by the invention can be up to 99.8%, and the purity can be up to 99%.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a preparation method of estolide.
Background
Organic esters are derivatives of carboxylic acids, and are classified into short-chain esters and long-chain esters in the range of 8 carbon atoms in total. Due to the characteristics of good solubility, wettability, lubricity, thermal stability, aroma and the like, the estolide is widely applied to chemical industries such as cosmetics, medicines, health products, lubricants, coatings, woodware coatings, aromatic products and the like. Among them, isobutyl isobutyrate, butyl hexanoate, isoamyl hexanoate, octyl octanoate, ethyl decanoate, ethyl dodecanoate, ethyl tetradecanoate, ethyl hexadecanoate and ethyl octadecanoate are typical long-chain esters having 8 or more carbon atoms, and are edible flavors and additives having fruit fragrance widely used in daily life. In addition, the estolide is widely applied in the field of renewable clean energy, for example, ethyl palmitate and ethyl stearate are one of the main components of the green energy biodiesel, have the advantages of good environmental protection, good fuel performance and the like, and have important strategic significance for controlling urban atmospheric pollution.
The traditional long-chain ester synthesis usually adopts a Fischer esterification method, namely, concentrated sulfuric acid is used as a catalyst to catalyze carboxylic acid and alcohol to react to generate ester under the condition of heating and refluxing. However, the preparation method has many problems to be solved, such as more side reactions, low product purity and yield, etc. To solve these problems, the related research in the literature has mainly focused on the use of catalystsFor improving the study, e.g. by using SO4 2-/MxOySolid acid catalysts, heteropolyacid catalysts, acidic ion resins, and the like, but the yield and purity of the product obtained by using the above catalysts are not satisfactory. Therefore, the research on the preparation method of the estolide to improve the product purity and yield of the estolide becomes a key research direction in the field of esterification reaction.
Disclosure of Invention
The invention provides a preparation method of estolide, and the yield and purity of the estolide prepared by the preparation method are high, the yield can reach 99.8%, and the purity can reach 99%.
The invention provides a preparation method of estolide, which comprises the following steps:
(1) carboxylic acid and alcohol are subjected to esterification reaction under the action of a catalyst; standing and layering the reaction solution to obtain a long-chain ester phase and a water phase; the catalyst comprises an ionic liquid or a eutectic solvent;
(2) purifying the long-chain ester phase obtained in the step (1), and separating to obtain high-purity long-chain ester; and (2) removing water in the water phase obtained in the step (1), and introducing the residual substances into the reaction system in the step (1) for esterification.
Preferably, the cation of the ionic liquid in the step (1) comprises an imidazolium cation, and the imidazolium cation has a structure shown as a formula I, a formula II or a formula III; the anion of the ionic liquid comprises chloride ion, bromide ion, iodide ion, tetrafluoroborate ion, hydrogen sulfate ion or hydrogen phosphate ion;
the R is1、R2Independently is C2～C10Alkyl groups of (a); r3SO3H is C2～C10An alkylsulfonic acid group of (a).
Preferably, said R is1、R2Independently is ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-butylPentyl, isopentyl, n-hexyl, 2-methylpentyl or 3-methylpentyl; the R is3SO3H is ethyl sulfonic acid group, n-propyl sulfonic acid group, isopropyl sulfonic acid group, n-butyl sulfonic acid group, isobutyl sulfonic acid group, n-pentyl sulfonic acid group, isopentyl sulfonic acid group, n-hexyl sulfonic acid group, 2-methyl pentyl sulfonic acid group or 3-methyl pentyl sulfonic acid group.
Preferably, the ionic liquid comprises one or more of 1-butyl-3-methylimidazole hydrogen sulfate, 1-butyl-3-methylimidazole dihydrogen phosphate and 1-butylsulfonic acid-3-methylimidazole hydrogen sulfate.
Preferably, the eutectic solvent in the step (1) consists of a hydrogen bond acceptor and a hydrogen bond donor, and the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is 1: 1-1: 5; the hydrogen bond acceptor comprises imidazole or quaternary ammonium salt, and the quaternary ammonium salt has a structure shown in a formula IV; the hydrogen bond donor comprises p-toluenesulfonic acid;
the R is4Is C2～C10Alkyl, cycloalkyl or aryl of (A), said X-Is a methanesulfonate anion or a p-toluenesulfonate anion.
Preferably, said R is4Is n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, n-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 3-ethylhexyl, cyclopentyl, cyclohexyl or benzyl.
Preferably, the eutectic solvent includes one or more of an imidazole-p-toluenesulfonic acid eutectic solvent, a trimethylcyclohexylammonium methanesulfonate-p-toluenesulfonic acid eutectic solvent, and an octyltrimethylammonium methanesulfonate-p-toluenesulfonic acid eutectic solvent.
Preferably, the carboxylic acid in step (1) comprises butyric acid, isobutyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid or stearic acid; the alcohol includes methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, n-hexanol, 2-hexanol, 3-hexanol, n-heptanol, 2-heptanol, 3-heptanol, n-octanol, 2-octanol, 3-octanol, 4-octanol; the molar ratio of the carboxylic acid to the alcohol is 0.01-10: 1.
Preferably, the esterification reaction in the step (1) is carried out at the temperature of 30-220 ℃ for 0.5-48 h; and the standing and layering time is 0.5-48 h.
Preferably, the method for removing water in the water phase in the step (2) comprises the following steps:
(a) distilling the aqueous phase to obtain a mixture of carboxylic acid, alcohol, estolide and water at the top of the distillation apparatus; obtaining ionic liquid or eutectic solvent at the bottom of a distillation device;
(b) rectifying the mixture obtained in the step (a) in an alcohol recovery tower to obtain alcohol at the top of the alcohol recovery tower and obtain a mixture of carboxylic acid, estolide and water at the bottom of the alcohol recovery tower;
(c) rectifying the mixture obtained in the step (b) in a carboxylic acid recovery tower to obtain water as a by-product at the top of the carboxylic acid recovery tower and obtain carboxylic acid and estolide at the bottom of the carboxylic acid recovery tower;
returning the ionic liquid or the eutectic solvent obtained from the bottom of the distillation device in the step (a), the alcohol obtained from the top of the alcohol recovery tower in the step (b) and the carboxylic acid and the long-chain ester obtained from the bottom of the carboxylic acid recovery tower in the step (c) to the step (1) for continuous esterification; removing water as a by-product obtained at the top of the carboxylic acid recovery column of step (c).
The invention provides a preparation method of estolide, which comprises the following steps: carboxylic acid and alcohol are subjected to esterification reaction under the presence of a catalyst; standing and layering the reaction solution to obtain a long-chain ester phase and a water phase; the catalyst comprises an ionic liquid or a eutectic solvent; purifying the long-chain ester phase, and separating to obtain high-purity long-chain ester; and (4) removing water in the water phase, and introducing the residual substances into an esterification reaction system to perform esterification reaction.
In the invention, the ionic liquid or the eutectic solvent has two functions, namely, the ionic liquid or the eutectic solvent is used as a catalyst to catalyze the esterification reaction; and the water in the reaction liquid can be separated from the estolide as an extractant, the estolide is separated from the reaction liquid, the forward reaction is promoted, and the yield of the estolide is improved.
The ionic liquid or the eutectic solvent provided by the invention has an extraction separation effect (equivalent to the separation and purification in advance of a microscopic system) in the stirring reaction process as an extractant, and can extract impurities (unreacted carboxylic acid and alcohol) in a long-chain ester phase obtained after standing and phase splitting into a water phase, so that the impurity content in the long-chain ester phase is low, and the purity of the obtained long-chain ester is improved; and then, the long-chain ester phase obtained after standing is distilled or washed by water, so that the purity of the long-chain ester is further improved, and the long-chain ester with higher purity can be obtained by the method provided by the application.
In addition, other reasons for the improvement of yield and purity are: compared with the traditional method in which concentrated sulfuric acid is used as a catalyst, the ionic liquid or the eutectic solvent has no oxidation, so that no side reaction is generated in the reaction process; secondly, the invention recycles the raw materials for reaction respectively for the long-chain ester phase obtained by standing and layering and the unreacted carboxylic acid and alcohol contained in the water phase, so that the recovered carboxylic acid and alcohol continuously participate in the esterification reaction, thereby further improving the yield and the purity of the method.
The results of the examples show that the yield and the purity of the estolide provided by the invention are high, the yield of the prepared isobutyl isobutyrate is 98.7-99.8%, and the purity is 90.65-99%; the yield of butyl caproate is 98.9-99.5%, and the purity is 91.05-94.23%; the yield of the isoamyl hexanoate is 99.0 to 99.5 percent, and the purity is 90.82 to 96.61 percent; the yield of octyl octanoate is 99.1 percent, and the purity is 93 percent; the yield of the methyl decanoate is 99.5 percent, and the purity is 94 percent; the yield of the ethyl dodecanoate is 99.3 percent, and the purity is 91 percent; the yield of the ethyl myristate was 99.2%, and the purity was 92%; the yield of the ethyl palmitate is 99.0 percent, and the purity is 93 percent; the yield of ethyl octadecanoate is 98.7%, and the purity is 97%.
Drawings
FIG. 1 is a flow diagram of a process for the preparation of estolides;
FIG. 2 is a flow diagram of a process for making estolides;
FIG. 3 is a Fourier transform infrared spectrum of an imidazole-p-toluenesulfonic acid eutectic solvent.
Detailed Description
The invention provides a preparation method of estolide, which comprises the following steps:
(1) carboxylic acid and alcohol are subjected to esterification reaction under the action of a catalyst; standing and layering the reaction solution to obtain a long-chain ester phase and a water phase; the catalyst comprises an ionic liquid or a eutectic solvent;
(2) purifying the long-chain ester phase obtained in the step (1), and separating to obtain high-purity long-chain ester; and (2) removing water in the water phase obtained in the step (1), and introducing the residual substances into the reaction system in the step (1) for esterification.
The invention carries out esterification reaction on carboxylic acid and alcohol under the catalyst; standing and layering the reaction solution to obtain a long-chain ester phase and a water phase.
In the present invention, the catalyst includes an ionic liquid or a eutectic solvent.
In the invention, the cation of the ionic liquid preferably comprises an imidazole cation, and the structure of the imidazole cation is shown as formula I, formula II or formula III; the anion of the ionic liquid preferably includes chloride ion, bromide ion, iodide ion, tetrafluoroborate ion, bisulfate ion, or hydrogenphosphate ion;
in the present invention, said R1、R2Independently is preferably C2～C10Further preferably C2～C6More preferably ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, 2-methylpentyl or 3-methylpentyl; said R is3SO3H is preferably C2～C10Alkyl sulfonic acid group of (2), further C2～C6More preferably an ethylsulfonic acid group, a n-propylsulfonic acid group, an isopropylsulfonic acid group, a n-butylsulfonic acid group, an isobutylsulfonic acid group, a n-pentylsulfonic acid group, an isopentylsulfonic acid group, a n-hexylsulfonic acid group, a 2-methylpentylsulfonic acid group or a 3-methylpentylsulfonic acid group.
In the present invention, the ionic liquid preferably includes one or more of 1-butyl-3-methylimidazole hydrogen sulfate, 1-butyl-3-methylimidazole dihydrogen phosphate, and 1-butylsulfonic acid-3-methylimidazole hydrogen sulfate.
In the invention, the eutectic solvent consists of a hydrogen bond acceptor and a hydrogen bond donor, and the molar ratio of the hydrogen bond acceptor to the hydrogen bond donor is preferably 1: 1-1: 5, more preferably 1: 2-1: 3, and more preferably 1: 2; the hydrogen bond acceptor preferably comprises imidazole or quaternary ammonium salt, the quaternary ammonium salt has a structure shown in a formula IV, and the imidazole has a structure shown in a formula V; the hydrogen bond donor preferably comprises p-toluenesulfonic acid, the hydrogen bond donor having a structure represented by formula VI:
in the formula IV, R4Preferably C2～C10Is more preferably C2～C6More preferably n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, n-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 3-ethylhexyl, cyclopentyl, cyclohexyl or benzyl; said X-Preferably a methanesulfonate anion or a p-toluenesulfonate anion.
In the present invention, the eutectic solvent preferably includes one or more of an imidazole-p-toluenesulfonic acid eutectic solvent, a trimethylcyclohexylammonium methanesulfonate-p-toluenesulfonic acid eutectic solvent, and an octyltrimethylammonium methanesulfonate-p-toluenesulfonic acid eutectic solvent.
In the invention, the ionic liquid in the technical scheme is a commercially available product. In the present invention, the eutectic solvent is prepared according to a conventional method in the art, and may be prepared according to the following method.
In the present invention, the preparation method of the imidazole-p-toluenesulfonic acid eutectic solvent preferably comprises the steps of: (1) carrying out vacuum drying pretreatment on imidazole and p-toluenesulfonic acid raw materials at 80 ℃ for 24h, (2) carrying out vacuum drying pretreatment on the dried imidazole and p-toluenesulfonic acid according to a molar ratio of 1:2, placing the mixture into a stirring reaction kettle, heating and stirring the mixture for 30min at the temperature of 80 ℃ and the stirring speed of 800rpm to form a colorless homogeneous liquid imidazole-p-toluenesulfonic acid eutectic solvent.
In the invention, the ionic liquid or the eutectic solvent has two functions, namely, the ionic liquid or the eutectic solvent is used as a catalyst to catalyze the esterification reaction; secondly, the water in the reaction liquid can be separated from the long-chain ester as an extractant, the long-chain ester is separated from the reaction liquid, and the forward reaction is promoted; in addition, through subsequent treatment, water in the water phase obtained by standing and layering is removed, and then carboxylic acid and alcohol which do not participate in the reaction in the water phase are returned to the esterification reaction to participate in the reaction, so that the yield of the esterification reaction is effectively improved.
The invention carries out esterification reaction on carboxylic acid and alcohol under the action of a catalyst to obtain reaction liquid.
In the present invention, the carboxylic acid preferably includes butyric acid, isobutyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, or stearic acid; the alcohol preferably includes methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, n-hexanol, 2-hexanol, 3-hexanol, n-heptanol, 2-heptanol, 3-heptanol, n-octanol, 2-octanol, 3-octanol, 4-octanol; the molar ratio of the carboxylic acid to the alcohol is preferably 0.01 to 10:1, more preferably 0.1 to 8:1, and still more preferably 0.5 to 2: 1.
In the invention, the temperature of the esterification reaction is preferably 30-220 ℃, more preferably 40-200 ℃, more preferably 50-150 ℃, and most preferably 50-95 ℃; the esterification reaction time is preferably 0.5-48 h, more preferably 1.0-40 h, even more preferably 1.5-35 h, and most preferably 2-6 h.
After the esterification reaction is finished, the reaction solution is kept stand for layering to obtain a long-chain ester phase and a water phase.
In the invention, the temperature of the standing layering is preferably 30-220 ℃, further preferably 40-200 ℃, more preferably 50-150 ℃, and most preferably 50-95 ℃; the standing and layering time is preferably 0.5-48 h, more preferably 1.0-40 h, even more preferably 1.5-35 h, and most preferably 2-6 h.
After standing and layering, the reaction solution is divided into two phases, and the upper layer is a long-chain ester phase; the lower layer is a water phase. In the present invention, the long-chain ester phase mainly comprises a long-chain ester, and a small amount of an ionic liquid or a eutectic solvent. In the present invention, the aqueous phase comprises mainly water, ionic liquid or eutectic solvent and unreacted carboxylic acid and alcohol, and a small amount of estolide.
The invention carries out distillation or water washing treatment on the long-chain ester phase obtained by standing and layering to obtain the high-purity long-chain ester.
In the present invention, the long-chain ester preferably includes isobutyl isobutyrate, butyl hexanoate, isoamyl hexanoate, octyl octanoate, ethyl decanoate, ethyl dodecanoate, ethyl tetradecanoate, ethyl hexadecanoate or ethyl octadecanoate.
In the present invention, the distillation preferably comprises flash distillation or vacuum distillation; in the invention, the distillation pressure is preferably 0.01-0.1 bar, more preferably 0.01-0.08 bar, and even more preferably 0.01-0.06 bar; the distillation temperature is preferably 50-250 ℃, more preferably 70-200 ℃, and even more preferably 100-150 ℃. The invention distills the long-chain ester phase to obtain high-purity long-chain ester at the top of the distillation device and obtain ionic liquid or eutectic solvent at the bottom of the distillation device. The invention preferably returns the ionic liquid or the eutectic solvent obtained at the bottom of the distillation device to the esterification reaction system for recycling.
The invention can also purify the long-chain ester phase by washing treatment. The present invention does not require any particular embodiment of the water wash, and may be practiced in a manner well known to those skilled in the art. The invention carries out water washing treatment on the long-chain ester phase, obtains the high-purity long-chain ester at the top of a water washing device, and obtains the mixture of the ionic liquid or the eutectic solvent and water at the bottom of the water washing device. The ionic liquid or the mixture of the eutectic solvent and the water obtained from the bottom of the water washing device is preferably removed with water and then returned to the esterification reaction system for recycling.
The invention preferably distills the water phase obtained by standing and layering, and removes water in the water phase to promote forward movement of the esterification reaction.
According to the invention, the ionic liquid obtained by washing and purifying the long-chain ester phase with water or the mixture of the eutectic solvent and water is combined with the water phase obtained by standing and layering, and then distillation is carried out. In the embodiment of the invention shown in fig. 2, the ionic liquid or the eutectic solvent and water mixture at the bottom of the water wash tank is introduced into the flash tank.
In the present invention, the method of removing water from the aqueous phase preferably comprises the steps of:
(a) distilling the aqueous phase to obtain a mixture of carboxylic acid, alcohol, estolide and water at the top of the distillation apparatus; obtaining ionic liquid or eutectic solvent at the bottom of a distillation device;
(b) rectifying the mixture obtained in the step (a) in an alcohol recovery tower to obtain alcohol at the top of the alcohol recovery tower and obtain a mixture of carboxylic acid, estolide and water at the bottom of the alcohol recovery tower;
(c) rectifying the mixture obtained in the step (b) in a carboxylic acid recovery tower to obtain water as a by-product at the top of the carboxylic acid recovery tower and obtain carboxylic acid and estolide at the bottom of the carboxylic acid recovery tower;
returning the ionic liquid or the eutectic solvent obtained from the bottom of the distillation device in the step (a), the alcohol obtained from the top of the alcohol recovery tower in the step (b) and the carboxylic acid and the long-chain ester obtained from the bottom of the carboxylic acid recovery tower in the step (c) to the step (1) for continuous reaction; removing water as a by-product obtained at the top of the carboxylic acid recovery column of step (c).
The aqueous phase is subjected to distillation, preferably comprising flash distillation or distillation under reduced pressure; the distillation pressure is preferably 0.001-0.1 bar, and more preferably 0.001-0.05 bar; the distillation temperature is preferably 50-300 ℃, more preferably 100-250 ℃, and even more preferably 150-200 ℃. The water phase is distilled, and a mixture of carboxylic acid, alcohol, estolide and water is obtained at the top of a distillation device; and obtaining the ionic liquid or the eutectic solvent at the bottom of the distillation device.
The invention carries out rectification treatment on the mixture of carboxylic acid, alcohol, long-chain ester and water obtained by distilling the water phase in an alcohol recovery tower. In the invention, the number of the tower plates of the alcohol recovery tower is preferably 10-60, more preferably 18-55, and even more preferably 25-45; the reflux ratio of the alcohol recovery tower is preferably 3-8, more preferably 3.5-6, and even more preferably 4.0-5.0. The invention obtains alcohol at the top of the alcohol recovery tower and a mixture of carboxylic acid, estolide and water at the bottom of the alcohol recovery tower. In the present invention, it is preferable that the alcohol obtained from the top of the alcohol recovery column is returned to the esterification reaction system after heat exchange treatment. The invention preferably adopts heat exchange treatment, which is beneficial to fully utilizing the heat of the alcohol obtained by rectification and simultaneously beneficial to avoiding the generation of byproducts when the alcohol with overhigh temperature enters an esterification reaction system. The present invention does not require any particular embodiment of the heat exchange process, and may be performed by a heat exchange process commonly known to those skilled in the art.
The mixture of carboxylic acid, long-chain ester and water obtained from the bottom of the alcohol recovery tower is rectified in the carboxylic acid recovery tower. In the invention, the number of the plates of the carboxylic acid recovery tower is preferably 10 to 60, more preferably 15 to 60, and even more preferably 20 to 60; the reflux ratio of the carboxylic acid recovery tower is preferably 1-5, more preferably 1.5-4.5, and even more preferably 2.0-4.0. The method obtains the byproduct water at the top of the carboxylic acid recovery tower, and obtains the carboxylic acid and the long-chain ester at the bottom of the carboxylic acid recovery tower. The invention preferably removes the byproduct water obtained at the top of the carboxylic acid recovery tower, which is beneficial to promoting the forward progress of the esterification reaction. In the present invention, it is preferable that the carboxylic acid and the long-chain ester obtained from the bottom of the carboxylic acid recovery column are subjected to heat exchange treatment and then returned to the esterification reaction system. The invention preferably adopts heat exchange treatment, which is beneficial to fully utilizing the heat of the carboxylic acid and the long-chain ester obtained by rectification and simultaneously beneficial to avoiding the generation of byproducts when the carboxylic acid and the long-chain ester with overhigh temperature enter an esterification reaction system. The present invention does not require any particular embodiment of the heat exchange process, and may be performed by a heat exchange process commonly known to those skilled in the art.
In the present invention, the preparation process flow chart of the estolide is shown in fig. 1 and fig. 2. Wherein FIG. 1 is a flow diagram of a process for the preparation of long chain esters by distillation to purify the long chain ester phase; FIG. 2 is a flow chart of the process for the preparation of long chain esters by purification of the long chain ester phase by water washing. In fig. 1 and 2, IL represents an ionic liquid or a eutectic solvent. As can be seen from FIGS. 1 and 2, the preparation method provided by the invention removes estolide and water from the reaction system, and other substances can be recycled, thereby effectively improving the yield and purity of estolide.
In the prior art, in the esterification reaction process, in order to ensure that the esterification reaction always has a forward driving force and improve the conversion rate of carboxylic acid or alcohol, an additional water-carrying agent such as cyclohexane, benzene, toluene, xylene and the like is mostly needed to be added, and then a water separator is utilized to separate an azeotrope of water and the water-carrying agent so as to timely remove generated water out of a reaction system, so as to promote the forward proceeding of the esterification reaction, but the water-carrying agent needs to be additionally separated from a reaction liquid after the water-carrying agent is added, so that the post-treatment difficulty of the reaction liquid is improved. The method is preferably adopted to remove the long-chain ester in the reaction system, and the water in the water phase obtained by standing and layering is removed through subsequent treatment, so that the forward proceeding of the esterification reaction is promoted, and the problem of increasing the post-treatment difficulty due to the use of a water-carrying agent is solved.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
According to the flow chart in FIG. 1, 3mol of isobutyric acid, 2.5mol of isobutanol, and 16.5mol of ionic liquid 1-butyl-3-methylimidazole hydrogensulfate were added to an esterification reaction kettle, and the esterification reaction kettle was heated to 80 ℃ and stirred at normal pressure for reaction for 3 hours at a stirring speed of 1000 rpm. After the reaction, the reaction liquid is introduced into a decanter for standing and phase splitting, and the standing time is 3 hours. And respectively introducing upper-layer liquid (ester phase) and lower-layer liquid (water phase) obtained after phase separation in a decanter into a flash tank 1 and a flash tank 2, and then purifying product ester and recovering raw materials (mainly ionic liquid, carboxylic acid and alcohol). Wherein the operating pressure of the flash tank 1 is 0.01bar, the operating temperature is 70 ℃, the product isobutyl isobutyrate with the mass fraction of 99 percent, namely high-purity ester, is extracted from the top of the flash tank 1, and the ionic liquid with the mass fraction of 99.99 percent is extracted from the bottom; the operating pressure of the flash tank 2 is 0.01bar, the operating temperature is 150 ℃, unreacted raw materials and a mixture containing water and ester are extracted from the top of the flash tank 2, and the ionic liquid with the mass fraction of 99.99% is extracted from the bottom. And the ionic liquid obtained from the bottoms of the flash tanks 1 and 2 is respectively subjected to heat exchange through a heat exchanger to 80 ℃, and then is returned to the esterification reaction kettle for cyclic utilization. And introducing the mixture extracted from the top of the flash tank 2 into an alcohol recovery tower, wherein the actual tower plate number of the alcohol recovery tower is 20, the operating pressure is normal pressure, the operating reflux ratio is 4.5, unreacted alcohol is obtained from the top of the alcohol recovery tower, and the unreacted alcohol is cooled to 80 ℃ by a heat exchanger and then returns to the esterification reaction kettle for recycling. Introducing the material in the tower kettle of the alcohol recovery tower into a carboxylic acid recovery tower, wherein the actual tower plate number of the carboxylic acid recovery tower is 16, the operating pressure is normal pressure, the operating reflux ratio is 2.5, obtaining byproduct water at the tower top of the acid recovery tower, finally removing water from an esterification reaction system, obtaining a mixed material containing unreacted carboxylic acid and partial product in the tower kettle of the acid recovery tower, cooling to 80 ℃ by a heat exchanger, and returning to the esterification reaction kettle for recycling. The yield of isobutyl isobutyrate in example 1 was 99.8% with a purity of 99%.
Example 2
The following treatment was also carried out according to the scheme of FIG. 1:
adding 2.5mol of isobutyric acid, 2.5mol of isobutanol and 3mol of ionic liquid 1-butyl-3-methylimidazole bisulfate into an esterification reaction kettle, heating the esterification reaction kettle to 80 ℃, and stirring and reacting for 3 hours at normal pressure, wherein the stirring speed is 1000 rpm. After the reaction, the reaction liquid is introduced into a decanter for standing and phase splitting, and the standing time is 3 hours. And respectively introducing upper-layer liquid (ester phase) and lower-layer liquid (water phase) obtained after phase separation in a decanter into a flash tank 1 and a flash tank 2, and then purifying product ester and recovering raw materials (mainly ionic liquid, carboxylic acid and alcohol). Wherein the operating pressure of the flash tank 1 is 0.06bar, the operating temperature is 140 ℃, the product isobutyl isobutyrate with the mass fraction of 91.73 percent, namely high-purity ester, is extracted from the top of the flash tank 1, and the ionic liquid with the mass fraction of 99.99 percent is extracted from the bottom; the operating pressure of the flash tank 2 is 0.01bar, the operating temperature is 150 ℃, unreacted raw materials and a mixture containing water and ester are extracted from the top of the flash tank 2, and the ionic liquid with the mass fraction of 99.99% is extracted from the bottom. And the ionic liquid obtained from the bottoms of the flash tanks 1 and 2 is respectively subjected to heat exchange through a heat exchanger to 80 ℃, and then is returned to the esterification reaction kettle for cyclic utilization. And introducing the mixture extracted from the top of the flash tank 2 into an alcohol recovery tower, wherein the actual tower plate number of the alcohol recovery tower is 18, the operating pressure is normal pressure, the operating reflux ratio is 5, unreacted alcohol is obtained from the top of the alcohol recovery tower, and the unreacted alcohol is cooled to 80 ℃ by a heat exchanger and then returns to the esterification reaction kettle for recycling. Introducing the material in the tower kettle of the alcohol recovery tower into a carboxylic acid recovery tower, wherein the actual tower plate number of the carboxylic acid recovery tower is 22, the operating pressure is normal pressure, the operating reflux ratio is 2, by-product water is obtained at the tower top of the acid recovery tower, finally water is removed from an esterification reaction system, the mixed material containing unreacted carboxylic acid and partial product is obtained in the tower kettle of the acid recovery tower, and the mixed material is cooled to 80 ℃ by a heat exchanger and then returned to the esterification reaction kettle for recycling. The yield of isobutyl isobutyrate in example 2 was 98.8% with a purity of 91.73%.
Example 3
The following treatment is carried out according to the flow of fig. 2:
adding 5mol of isobutyric acid, 2.5mol of isobutanol and 7.5mol of ionic liquid 1-butyl-3-methylimidazole dihydrogen phosphate into an esterification reaction kettle, heating the esterification reaction kettle to 70 ℃, and stirring and reacting for 3.5 hours at normal pressure, wherein the stirring speed is 1000 rpm. After the reaction, the reaction solution was introduced into a decanter for standing for phase separation for 3.5 hours. And respectively introducing the upper layer liquid (ester phase) and the lower layer liquid (water phase) obtained after phase separation in the decanter into a rinsing tank and a flash tank, and then purifying the product ester and recovering the raw materials (mainly ionic liquid, carboxylic acid and alcohol). Wherein the operation pressure of the rinsing bath is normal pressure, the operation temperature is room temperature, 93.73% by mass of the product isobutyl isobutyrate, namely high-purity ester, is extracted from the top of the rinsing bath, and the mixture of the ionic liquid and water is extracted from the bottom and introduced into a flash tank; the operating pressure of the flash tank is 0.01bar, the operating temperature is 150 ℃, unreacted raw materials and a mixture containing water and ester are extracted from the top of the flash tank, and 99.99% of ionic liquid by mass fraction is extracted from the bottom of the flash tank. And the ionic liquid obtained at the bottom of the flash tank is respectively subjected to heat exchange through a heat exchanger to 70 ℃, and then returns to the esterification reaction kettle for cyclic utilization. Introducing the mixture extracted from the top of the flash tank into an alcohol recovery tower, wherein the actual tower plate number of the alcohol recovery tower is 28, the operating pressure is normal pressure, the operating reflux ratio is 3.5, unreacted alcohol is obtained at the top of the alcohol recovery tower, and the unreacted alcohol is cooled to 70 ℃ by a heat exchanger and then returns to the esterification reaction kettle for recycling. Introducing the material in the tower kettle of the alcohol recovery tower into a carboxylic acid recovery tower, wherein the actual tower plate number of the carboxylic acid recovery tower is 35, the operating pressure is normal pressure, the operating reflux ratio is 1.5, obtaining byproduct water at the tower top of the acid recovery tower, finally removing water from an esterification reaction system, obtaining a mixed material containing unreacted carboxylic acid and partial product in the tower kettle of the acid recovery tower, cooling to 70 ℃ by a heat exchanger, and returning to the esterification reaction kettle for recycling. The yield of isobutyl isobutyrate in example 3 was 99.3% with a purity of 93.73%.
Example 4
The following treatment was carried out according to the flow of FIG. 1:
3.75mol of isobutyric acid, 2.5mol of isobutanol and 3.0mol of ionic liquid N-methylimidazolium chloride [ HMim ] Cl are added into an esterification reaction kettle, the esterification reaction kettle is heated to 60 ℃, and is stirred and reacted for 4 hours under normal pressure, and the stirring speed is 1000 rpm. After the reaction, the reaction liquid is introduced into a decanter for standing and phase splitting, and the standing time is 4 hours. And respectively introducing upper-layer liquid (ester phase) and lower-layer liquid (water phase) obtained after phase separation in a decanter into a flash tank 1 and a flash tank 2, and then purifying product ester and recovering raw materials (mainly ionic liquid, carboxylic acid and alcohol). Wherein the operating pressure of the flash tank 1 is 0.01bar, the operating temperature is 90 ℃, a product isobutyl isobutyrate with the mass fraction of 92.75 percent, namely high-purity ester, is extracted from the top of the flash tank 1, and ionic liquid with the mass fraction of 99.99 percent is extracted from the bottom of the flash tank 1; the operating pressure of the flash tank 2 is 0.01bar, the operating temperature is 150 ℃, unreacted raw materials and a mixture containing water and ester are extracted from the top of the flash tank 2, and the ionic liquid with the mass fraction of 99.99% is extracted from the bottom. And the ionic liquid obtained from the bottoms of the flash tanks 1 and 2 is respectively subjected to heat exchange through a heat exchanger to 60 ℃, and then is returned to the esterification reaction kettle for cyclic utilization. And introducing the mixture extracted from the top of the flash tank 2 into an alcohol recovery tower, wherein the actual tower plate number of the alcohol recovery tower is 26, the operating pressure is normal pressure, the operating reflux ratio is 4, unreacted alcohol is obtained from the top of the alcohol recovery tower, and the unreacted alcohol is cooled to 60 ℃ by a heat exchanger and then returns to the esterification reaction kettle for recycling. Introducing the material in the tower kettle of the alcohol recovery tower into a carboxylic acid recovery tower, wherein the actual tower plate number of the carboxylic acid recovery tower is 30, the operating pressure is normal pressure, the operating reflux ratio is 2, by-product water is obtained at the tower top of the acid recovery tower, finally water is removed from an esterification reaction system, the mixed material containing unreacted carboxylic acid and partial product is obtained in the tower kettle of the acid recovery tower, and the mixed material is cooled to 60 ℃ by a heat exchanger and then returned to the esterification reaction kettle for recycling. The yield of isobutyl isobutyrate in example 4 was 99.2% with a purity of 92.75%.
Example 5
The following treatment was carried out according to the flow of FIG. 1:
adding 0.75kmol of isobutyric acid, 0.75kmol of isobutanol and 0.45kmol of ionic liquid 1-butyl sulfonic acid-3-methyl imidazole bisulfate into an esterification reaction kettle, heating the esterification reaction kettle to 50 ℃, and stirring and reacting for 4.5 hours under normal pressure, wherein the stirring speed is 1000 rpm. After the reaction, the reaction solution was introduced into a decanter for standing for phase separation for 4.5 hours. And respectively introducing upper-layer liquid (ester phase) and lower-layer liquid (water phase) obtained after phase separation in a decanter into a flash tank 1 and a flash tank 2, and then purifying product ester and recovering raw materials (mainly ionic liquid, carboxylic acid and alcohol). Wherein the operating pressure of the flash tank 1 is 0.01bar, the operating temperature is 90 ℃, the product isobutyl isobutyrate with the mass fraction of 91.64 percent, namely high-purity ester, is extracted from the top of the flash tank 1, and the ionic liquid with the mass fraction of 99.99 percent is extracted from the bottom; the operating pressure of the flash tank 2 is 0.05bar, the operating temperature is 200 ℃, unreacted raw materials and a mixture containing water and ester are extracted from the top of the flash tank 2, and the ionic liquid with the mass fraction of 99.99% is extracted from the bottom. And the ionic liquid obtained from the bottoms of the flash tanks 1 and 2 is respectively subjected to heat exchange through a heat exchanger to 50 ℃, and then is returned to the esterification reaction kettle for cyclic utilization. And introducing the mixture extracted from the top of the flash tank 2 into an alcohol recovery tower, wherein the actual tower plate number of the alcohol recovery tower is 20, the operating pressure is normal pressure, the operating reflux ratio is 4.5, unreacted alcohol is obtained from the top of the alcohol recovery tower, and the unreacted alcohol is cooled to 50 ℃ by a heat exchanger and then returns to the esterification reaction kettle for recycling. Introducing the material in the tower kettle of the alcohol recovery tower into a carboxylic acid recovery tower, wherein the actual tower plate number of the carboxylic acid recovery tower is 25, the operating pressure is normal pressure, the operating reflux ratio is 2.8, obtaining byproduct water at the top of the acid recovery tower, finally removing water from an esterification reaction system, obtaining a mixed material containing unreacted carboxylic acid and partial product in the tower kettle of the acid recovery tower, cooling to 50 ℃ by a heat exchanger, and returning to the esterification reaction kettle for recycling. The yield of isobutyl isobutyrate in example 5 was 98.7% with a purity of 91.64%.
Example 6
The following treatment was carried out according to the flow of FIG. 1:
imidazole and p-toluenesulfonic acid are subjected to vacuum drying pretreatment for 24 hours at 80 ℃, the dried imidazole and p-toluenesulfonic acid are weighed according to the molar ratio of 1:2, the weighed imidazole and p-toluenesulfonic acid are placed in a stirring reaction kettle, and the mixture is heated and stirred for 30 minutes at 80 ℃ and at the stirring speed of 800rpm to form a colorless homogeneous liquid imidazole-p-toluenesulfonic acid eutectic solvent. 2.5mol of isobutyric acid, 2.5mol of isobutanol and 0.788mol of imidazole-p-toluenesulfonic acid eutectic solvent (the molar ratio of imidazole to p-toluenesulfonic acid is 1:2) are added into an esterification reaction kettle, the esterification reaction kettle is heated to 80 ℃, and the reaction is carried out for 3 hours under normal pressure with stirring at the rotating speed of 1000 rpm. After the reaction, the reaction liquid is introduced into a decanter for standing and phase splitting, and the standing time is 3 hours. And respectively introducing upper-layer liquid (ester phase) and lower-layer liquid (water phase) obtained after phase separation in a decanter into a flash tank 1 and a flash tank 2, and then purifying product ester and recovering raw materials (mainly ionic liquid, carboxylic acid and alcohol). Wherein the operating pressure of the flash tank 1 is 0.01bar, the operating temperature is 90 ℃, a product isobutyl isobutyrate with the mass fraction of 91.37 percent, namely high-purity ester, is extracted from the top of the flash tank 1, and a eutectic solvent with the mass fraction of 99.99 percent is extracted from the bottom of the flash tank 1; the operating pressure of the flash tank 2 is 0.03bar, the operating temperature is 180 ℃, unreacted raw materials and a mixture containing water and ester are extracted from the top of the flash tank 2, and a eutectic solvent with the mass fraction of 99.99% is extracted from the bottom. And the ionic liquid obtained from the bottoms of the flash tanks 1 and 2 is respectively subjected to heat exchange through a heat exchanger to 80 ℃, and then is returned to the esterification reaction kettle for cyclic utilization. And introducing the mixture extracted from the top of the flash tank 2 into an alcohol recovery tower, wherein the actual tower plate number of the alcohol recovery tower is 22, the operating pressure is normal pressure, the operating reflux ratio is 4.8, unreacted alcohol is obtained from the top of the alcohol recovery tower, and the unreacted alcohol is cooled to 80 ℃ by a heat exchanger and then returns to the esterification reaction kettle for recycling. Introducing the material in the tower kettle of the alcohol recovery tower into a carboxylic acid recovery tower, wherein the actual tower plate number of the carboxylic acid recovery tower is 28, the operating pressure is normal pressure, the operating reflux ratio is 2.4, obtaining byproduct water at the tower top of the acid recovery tower, finally removing water from an esterification reaction system, obtaining a mixed material containing unreacted carboxylic acid and partial product in the tower kettle of the acid recovery tower, cooling to 80 ℃ by a heat exchanger, and returning to the esterification reaction kettle for recycling. The yield of isobutyl isobutyrate in example 6 was 99.6% with a purity of 91.37%.
Wherein the Fourier transform infrared spectrum of the imidazole-p-toluenesulfonic acid eutectic solvent is shown in figure 3, and compared with the infrared spectrum of the imidazole and the p-toluenesulfonic acid alone, the spectrum of the imidazole-p-toluenesulfonic acid eutectic solvent is 2234cm-1New broad peak appears at the position, and the low wave number is 3406cm-1The characteristic peak shows that hydrogen bonds are formed between imidazole and p-toluenesulfonic acid, and shows that the imidazole and the p-toluenesulfonic acid form an imidazole-p-toluenesulfonic acid eutectic solvent.
It was confirmed that imidazole and p-toluenesulfonic acid formed an imidazole-p-toluenesulfonic acid eutectic solvent by measuring the melting point of the imidazole-p-toluenesulfonic acid eutectic solvent with a differential thermal scanner at 45.48 ℃ below the melting point of each of imidazole (melting point 92.63 ℃) and p-toluenesulfonic acid (melting point 104.50 ℃).
Example 7
The following treatment was carried out according to the flow of FIG. 1:
imidazole and p-toluenesulfonic acid are subjected to vacuum drying pretreatment for 24 hours at 80 ℃, then imidazole and p-toluenesulfonic acid are weighed according to the molar ratio of 1:2, the weighed imidazole and p-toluenesulfonic acid are placed in a stirring reaction kettle, and the mixture is heated and stirred for 30 minutes at 80 ℃ and at the stirring speed of 800rpm to form a colorless homogeneous liquid imidazole-p-toluenesulfonic acid eutectic solvent. Adding 3mol of isobutyric acid, 2.5mol of isobutanol and 0.654mol of imidazole-p-toluenesulfonic acid eutectic solvent (the molar ratio of imidazole to p-toluenesulfonic acid is 1:2) into an esterification reaction kettle, heating the esterification reaction kettle to 80 ℃, and stirring and reacting for 3 hours under normal pressure, wherein the stirring speed is 1000 rpm. After the reaction, the reaction liquid is introduced into a decanter for standing and phase splitting, and the standing time is 3 hours. And respectively introducing an upper layer liquid (ester phase) and a lower layer liquid (water phase) obtained after phase separation in the decanter into a flash tank 1 and a flash tank 2 for product ester purification and raw material (mainly eutectic solvent, carboxylic acid and alcohol) recovery. Wherein the operating pressure of the flash tank 1 is 0.01bar, the operating temperature is 90 ℃, a product isobutyl isobutyrate with the mass fraction of 90.65 percent, namely high-purity ester, is extracted from the top of the flash tank 1, and a eutectic solvent with the mass fraction of 99.99 percent is extracted from the bottom of the flash tank 1; the operating pressure of the flash tank 2 is 0.01bar, the operating temperature is 150 ℃, unreacted raw materials and a mixture containing water and ester are extracted from the top of the flash tank 2, and the ionic liquid with the mass fraction of 99.99% is extracted from the bottom. And the ionic liquid obtained from the bottoms of the flash tanks 1 and 2 is respectively subjected to heat exchange through a heat exchanger to 80 ℃, and then is returned to the esterification reaction kettle for cyclic utilization. And introducing the mixture extracted from the top of the flash tank 2 into an alcohol recovery tower, wherein the actual tower plate number of the alcohol recovery tower is 24, the operating pressure is normal pressure, the operating reflux ratio is 4.6, unreacted alcohol is obtained from the top of the alcohol recovery tower, and the unreacted alcohol is cooled to 80 ℃ by a heat exchanger and then returns to the esterification reaction kettle for recycling. Introducing the material in the tower kettle of the alcohol recovery tower into a carboxylic acid recovery tower, wherein the actual tower plate number of the carboxylic acid recovery tower is 30, the operating pressure is normal pressure, the operating reflux ratio is 2.1, obtaining byproduct water at the tower top of the acid recovery tower, finally removing water from an esterification reaction system, obtaining a mixed material containing unreacted carboxylic acid and partial product in the tower kettle of the acid recovery tower, cooling to 80 ℃ by a heat exchanger, and returning to the esterification reaction kettle for recycling. The yield of isobutyl isobutyrate in example 7 was 99.1% with a purity of 90.65%.
Example 8
The following treatment was carried out according to the flow of FIG. 1:
adding 2.5mol of caproic acid, 2.5mol of butanol and 2.151mol of ionic liquid 1-butyl-3-methylimidazole bisulfate into an esterification reaction kettle, heating the esterification reaction kettle to 95 ℃, and stirring and reacting for 2 hours under normal pressure, wherein the stirring speed is 1000 rpm. After the reaction, the reaction liquid is introduced into a decanter for standing and phase splitting, and the standing time is 2 hours. And respectively introducing upper-layer liquid (ester phase) and lower-layer liquid (water phase) obtained after phase separation in a decanter into a flash tank 1 and a flash tank 2, and then purifying product ester and recovering raw materials (mainly ionic liquid, carboxylic acid and alcohol). Wherein the operating pressure of the flash tank 1 is 0.01bar, the operating temperature is 95 ℃, a product butyl caproate with the mass fraction of 94.02 percent, namely high-purity ester, is extracted from the top of the flash tank 1, and ionic liquid with the mass fraction of 99.99 percent is extracted from the bottom of the flash tank 1; the operating pressure of the flash tank 2 is 0.01bar, the operating temperature is 150 ℃, unreacted raw materials and a mixture containing water and ester are extracted from the top of the flash tank 2, and the ionic liquid with the mass fraction of 99.99% is extracted from the bottom. And the ionic liquid obtained from the bottoms of the flash tanks 1 and 2 is respectively subjected to heat exchange through a heat exchanger to 95 ℃, and then is returned to the esterification reaction kettle for cyclic utilization. And introducing the mixture extracted from the top of the flash tank 2 into an alcohol recovery tower, wherein the actual tower plate number of the alcohol recovery tower is 28, the operating pressure is normal pressure, the operating reflux ratio is 4.6, unreacted alcohol is obtained from the top of the alcohol recovery tower, and the unreacted alcohol is cooled to 95 ℃ by a heat exchanger and then returns to the esterification reaction kettle for recycling. Introducing the material in the tower kettle of the alcohol recovery tower into a carboxylic acid recovery tower, wherein the actual tower plate number of the carboxylic acid recovery tower is 35, the operating pressure is normal pressure, the operating reflux ratio is 2.6, obtaining byproduct water at the top of the acid recovery tower, finally removing water from an esterification reaction system, obtaining a mixed material containing unreacted carboxylic acid and partial product in the tower kettle of the acid recovery tower, cooling to 95 ℃ by a heat exchanger, and returning to the esterification reaction kettle for recycling. The yield of butyl hexanoate in example 8 was 99.5% with a purity of 94.02%.
Example 9
The following treatment is carried out according to the flow of fig. 2:
2.5mol of caproic acid, 4.375mol of butanol and 1.229mol of ionic liquid 1-butyl-3-methylimidazole dihydrogen phosphate are added into an esterification reaction kettle, the esterification reaction kettle is heated to 95 ℃, and the stirring reaction is carried out for 2 hours under normal pressure, wherein the stirring speed is 1000 rpm. After the reaction, the reaction liquid is introduced into a decanter for standing and phase splitting, and the standing time is 2 hours. And respectively introducing the upper layer liquid (ester phase) and the lower layer liquid (water phase) obtained after phase separation in the decanter into a rinsing tank and a flash tank, and then purifying the product ester and recovering the raw materials (mainly ionic liquid, carboxylic acid and alcohol). Wherein the operation pressure of the rinsing bath is normal pressure, the operation temperature is room temperature, 91.05% by mass of butyl caproate, namely high-purity ester, is extracted from the top of the rinsing bath, and a mixture of ionic liquid and water is extracted from the bottom and introduced into a flash tank; the operating pressure of the flash tank is 0.01bar, the operating temperature is 160 ℃, unreacted raw materials and a mixture containing water and ester are extracted from the top of the flash tank, and 99.99% of ionic liquid by mass fraction is extracted from the bottom of the flash tank. And the ionic liquid obtained at the bottom of the flash tank is respectively subjected to heat exchange through a heat exchanger to 95 ℃, and then returns to the esterification reaction kettle for cyclic utilization. Introducing the mixture extracted from the top of the flash tank into an alcohol recovery tower, wherein the actual tower plate number of the alcohol recovery tower is 22, the operating pressure is normal pressure, the operating reflux ratio is 5.4, unreacted alcohol is obtained at the top of the alcohol recovery tower, and the unreacted alcohol is cooled to 95 ℃ by a heat exchanger and then returns to the esterification reaction kettle for recycling. Introducing the material in the tower kettle of the alcohol recovery tower into a carboxylic acid recovery tower, wherein the actual tower plate number of the carboxylic acid recovery tower is 30, the operating pressure is normal pressure, the operating reflux ratio is 3.1, obtaining byproduct water at the top of the acid recovery tower, finally removing water from an esterification reaction system, obtaining a mixed material containing unreacted carboxylic acid and partial product in the tower kettle of the acid recovery tower, cooling to 95 ℃ by a heat exchanger, and returning to the esterification reaction kettle for recycling. The yield of butyl hexanoate in example 9 was 98.9% with a purity of 91.05%.
Example 10
The following treatment was carried out according to the flow of FIG. 1:
adding 2.5mol of caproic acid, 3.75mol of butanol and 2.151mol of ionic liquid 1-butyl sulfonic acid-3-methylimidazole bisulfate into an esterification reaction kettle, heating the esterification reaction kettle to 95 ℃, and stirring and reacting for 2 hours under normal pressure, wherein the stirring speed is 1000 rpm. After the reaction, the reaction liquid is introduced into a decanter for standing and phase splitting, and the standing time is 2 hours. And respectively introducing upper-layer liquid (ester phase) and lower-layer liquid (water phase) obtained after phase separation in a decanter into a flash tank 1 and a flash tank 2, and then purifying product ester and recovering raw materials (mainly ionic liquid, carboxylic acid and alcohol). Wherein the operating pressure of the flash tank 1 is 0.01bar, the operating temperature is 95 ℃, 94.23% mass fraction of butyl caproate, namely high-purity ester, is extracted from the top of the flash tank 1, and 99.99% mass fraction of ionic liquid is extracted from the bottom; the operating pressure of the flash tank 2 is 0.01bar, the operating temperature is 160 ℃, unreacted raw materials and a mixture containing water and ester are extracted from the top of the flash tank 2, and the ionic liquid with the mass fraction of 99.99% is extracted from the bottom. And the ionic liquid obtained from the bottoms of the flash tanks 1 and 2 is respectively subjected to heat exchange through a heat exchanger to 95 ℃, and then is returned to the esterification reaction kettle for cyclic utilization. And introducing the mixture extracted from the top of the flash tank 2 into an alcohol recovery tower, wherein the actual tower plate number of the alcohol recovery tower is 25, the operating pressure is normal pressure, the operating reflux ratio is 5, unreacted alcohol is obtained from the top of the alcohol recovery tower, and the unreacted alcohol is cooled to 95 ℃ by a heat exchanger and then returns to the esterification reaction kettle for recycling. Introducing the material in the tower kettle of the alcohol recovery tower into a carboxylic acid recovery tower, wherein the actual tower plate number of the carboxylic acid recovery tower is 32, the operating pressure is normal pressure, the operating reflux ratio is 2.9, obtaining byproduct water at the tower top of the acid recovery tower, finally removing water from an esterification reaction system, obtaining a mixed material containing unreacted carboxylic acid and partial product in the tower kettle of the acid recovery tower, cooling to 95 ℃ by a heat exchanger, and returning to the esterification reaction kettle for recycling. The yield of butyl hexanoate in example 10 was 99.2% with a purity of 94.23%.
Example 11
The following treatment is carried out according to the flow of fig. 2:
2.5mol of caproic acid, 2.5mol of isoamyl alcohol and 1.229mol of ionic liquid N-methylimidazole bisulfate [ HMIm ] [ HSO4] are added into an esterification reaction kettle, the esterification reaction kettle is heated to 75 ℃, and is stirred and reacted for 3 hours under normal pressure, and the stirring speed is 1000 rpm. After the reaction, the reaction liquid is introduced into a decanter for standing and phase splitting, and the standing time is 3 hours. And respectively introducing the upper layer liquid (ester phase) and the lower layer liquid (water phase) obtained after phase separation in the decanter into a rinsing tank and a flash tank, and then purifying the product ester and recovering the raw materials (mainly ionic liquid, carboxylic acid and alcohol). Wherein the operation pressure of the rinsing bath is normal pressure, the operation temperature is room temperature, the product isoamyl hexanoate with the mass fraction of 93.56 percent, namely high-purity ester, is extracted from the top of the rinsing bath, and the mixture of the ionic liquid and water is extracted from the bottom and introduced into a flash tank; the operating pressure of the flash tank is 0.01bar, the operating temperature is 170 ℃, unreacted raw materials and a mixture containing water and ester are extracted from the top of the flash tank, and 99.99% of ionic liquid by mass fraction is extracted from the bottom of the flash tank. And the ionic liquid obtained from the bottom of the flash tank is respectively subjected to heat exchange through a heat exchanger to 75 ℃, and then returns to the esterification reaction kettle for cyclic utilization. Introducing the mixture extracted from the top of the flash tank into an alcohol recovery tower, wherein the actual tower plate number of the alcohol recovery tower is 25, the operating pressure is normal pressure, the operating reflux ratio is 4.8, unreacted alcohol is obtained at the top of the alcohol recovery tower, and the unreacted alcohol is cooled to 75 ℃ by a heat exchanger and then returns to the esterification reaction kettle for recycling. Introducing the material in the tower kettle of the alcohol recovery tower into a carboxylic acid recovery tower, wherein the actual tower plate number of the carboxylic acid recovery tower is 30, the operating pressure is normal pressure, the operating reflux ratio is 3.5, obtaining byproduct water at the top of the acid recovery tower, finally removing water from an esterification reaction system, obtaining a mixed material containing unreacted carboxylic acid and partial product in the tower kettle of the acid recovery tower, cooling to 75 ℃ by a heat exchanger, and returning to the esterification reaction kettle for recycling. The yield of isoamyl hexanoates in example 11 was 99.4% with a purity of 93.56%.
Example 12
The following treatment is carried out according to the flow of fig. 2:
2.5mol of caproic acid, 2.5mol of isoamyl alcohol and 1.598mol of ionic liquid 1-butyl-3-methyl imidazole dihydric phosphate are added into an esterification reaction kettle, the esterification reaction kettle is heated to 95 ℃, and is stirred and reacted for 2 hours under normal pressure, and the stirring speed is 1000 rpm. After the reaction, the reaction liquid is introduced into a decanter for standing and phase splitting, and the standing time is 2 hours. And respectively introducing the upper layer liquid (ester phase) and the lower layer liquid (water phase) obtained after phase separation in the decanter into a rinsing tank and a flash tank, and then purifying the product ester and recovering the raw materials (mainly ionic liquid, carboxylic acid and alcohol). Wherein the operation pressure of the rinsing bath is normal pressure, the operation temperature is room temperature, isoamyl hexanoate with the mass fraction of 96.61 percent is extracted from the top of the rinsing bath, namely high-purity ester, and the mixture of ionic liquid and water is extracted from the bottom and introduced into a flash tank; the operating pressure of the flash tank is 0.01bar, the operating temperature is 170 ℃, unreacted raw materials and a mixture containing water and ester are extracted from the top of the flash tank, and 99.99% of ionic liquid by mass fraction is extracted from the bottom of the flash tank. And the ionic liquid obtained at the bottom of the flash tank is respectively subjected to heat exchange through a heat exchanger to 95 ℃, and then returns to the esterification reaction kettle for cyclic utilization. Introducing the mixture extracted from the top of the flash tank into an alcohol recovery tower, wherein the actual tower plate number of the alcohol recovery tower is 25, the operating pressure is normal pressure, the operating reflux ratio is 4.8, unreacted alcohol is obtained at the top of the alcohol recovery tower, and the unreacted alcohol is cooled to 95 ℃ by a heat exchanger and then returns to the esterification reaction kettle for recycling. Introducing the material in the tower kettle of the alcohol recovery tower into a carboxylic acid recovery tower, wherein the actual tower plate number of the carboxylic acid recovery tower is 30, the operating pressure is normal pressure, the operating reflux ratio is 3.5, obtaining byproduct water at the top of the acid recovery tower, finally removing water from an esterification reaction system, obtaining a mixed material containing unreacted carboxylic acid and partial product in the tower kettle of the acid recovery tower, cooling to 95 ℃ by a heat exchanger, and returning to the esterification reaction kettle for recycling. The yield of isoamyl hexanoates in example 12 was 99.5% with a purity of 96.61%.
Example 13
The following treatment is carried out according to the flow of fig. 2:
adding 2.5mol of caproic acid, 2.5mol of isoamyl alcohol and 1.598mol of ionic liquid 1-butyl sulfonic acid-3-methyl imidazole bisulfate into an esterification reaction kettle, heating the esterification reaction kettle to 65 ℃, and stirring and reacting for 4 hours under normal pressure, wherein the stirring speed is 1000 rpm. After the reaction, the reaction liquid is introduced into a decanter for standing and phase splitting, and the standing time is 4 hours. And respectively introducing the upper layer liquid (ester phase) and the lower layer liquid (water phase) obtained after phase separation in the decanter into a rinsing tank and a flash tank, and then purifying the product ester and recovering the raw materials (mainly ionic liquid, carboxylic acid and alcohol). Wherein the operation pressure of the rinsing bath is normal pressure, the operation temperature is room temperature, the product isoamyl hexanoate with the mass fraction of 90.82 percent, namely high-purity ester, is extracted from the top of the rinsing bath, and the mixture of the ionic liquid and water is extracted from the bottom and introduced into a flash tank; the operating pressure of the flash tank is 0.01bar, the operating temperature is 170 ℃, unreacted raw materials and a mixture containing water and ester are extracted from the top of the flash tank, and 99.99% of ionic liquid by mass fraction is extracted from the bottom of the flash tank. And the ionic liquid obtained from the bottom of the flash tank is respectively subjected to heat exchange through a heat exchanger to 65 ℃, and then returns to the esterification reaction kettle for cyclic utilization. Introducing the mixture extracted from the top of the flash tank into an alcohol recovery tower, wherein the actual tower plate number of the alcohol recovery tower is 25, the operating pressure is normal pressure, the operating reflux ratio is 4.8, unreacted alcohol is obtained at the top of the alcohol recovery tower, and the unreacted alcohol is cooled to 65 ℃ by a heat exchanger and then returns to the esterification reaction kettle for recycling. Introducing the material in the tower kettle of the alcohol recovery tower into a carboxylic acid recovery tower, wherein the actual tower plate number of the carboxylic acid recovery tower is 30, the operating pressure is normal pressure, the operating reflux ratio is 3.5, obtaining byproduct water at the tower top of the acid recovery tower, finally removing water from an esterification reaction system, obtaining a mixed material containing unreacted carboxylic acid and partial product in the tower kettle of the acid recovery tower, cooling to 65 ℃ by a heat exchanger, and returning to the esterification reaction kettle for recycling. The yield of isoamyl hexanoate in example 13 was 99.0% and the purity was 90.82%.
Example 14
The following treatment is carried out according to the flow of fig. 2:
adding 2.5mol of n-octanoic acid, 2.5mol of n-octanol and 0.75mol of trimethyl cyclohexyl ammonium methanesulfonate-p-toluenesulfonic acid eutectic solvent (the molar ratio of trimethyl cyclohexyl ammonium methanesulfonate to p-toluenesulfonic acid is 1:2) into an esterification reaction kettle, heating the esterification reaction kettle to 80 ℃, and stirring and reacting for 3.5h under normal pressure at the stirring speed of 1000 rpm. After the reaction, the reaction solution was introduced into a decanter for standing for phase separation for 3.5 hours. And respectively introducing an upper layer liquid (ester phase) and a lower layer liquid (water phase) obtained after phase separation in a decanter into a rinsing bath and a flash tank, and then purifying the product ester and recovering raw materials (mainly eutectic solvent, carboxylic acid and alcohol). Wherein the operation pressure of the rinsing bath is normal pressure, the operation temperature is room temperature, the product octyl octanoate with the mass fraction of 93 percent, namely high-purity ester, is extracted from the top of the rinsing bath, and the mixture of the eutectic solvent and water is extracted from the bottom and introduced into a flash tank; the operating pressure of the flash tank is 0.001bar, the operating temperature is 100 ℃, unreacted raw materials and a mixture containing water and ester are extracted from the top of the flash tank, and a eutectic solvent with the mass fraction of 99.99% is extracted from the bottom of the flash tank. The eutectic solvent obtained at the bottom of the flash tank is respectively subjected to heat exchange through a heat exchanger to 80 ℃ and then returns to the esterification reaction kettle for cyclic utilization. Introducing the mixture extracted from the top of the flash tank into an alcohol recovery tower, wherein the actual tower plate number of the alcohol recovery tower is 30, the operating pressure is normal pressure, the operating reflux ratio is 5, unreacted alcohol is obtained from the top of the alcohol recovery tower, and the unreacted alcohol is cooled to 80 ℃ by a heat exchanger and then returns to the esterification reaction kettle for recycling. Introducing the material in the tower kettle of the alcohol recovery tower into a carboxylic acid recovery tower, wherein the actual tower plate number of the carboxylic acid recovery tower is 35, the operating pressure is normal pressure, the operating reflux ratio is 4, by-product water is obtained at the tower top of the acid recovery tower, finally water is removed from an esterification reaction system, the mixed material containing unreacted carboxylic acid and partial product is obtained in the tower kettle of the acid recovery tower, and the mixed material is cooled to 80 ℃ by a heat exchanger and then returned to the esterification reaction kettle for recycling. The yield of octyl octanoate in example 14 was 99.1% and the purity was 93%.
Example 15
The following treatment is carried out according to the flow of fig. 2:
adding 2.5mol of capric acid, 5.0mol of methanol and 0.75mol of trimethyl cyclohexyl ammonium methanesulfonate-p-toluenesulfonic acid eutectic solvent (the molar ratio of trimethyl cyclohexyl ammonium methanesulfonate to p-toluenesulfonic acid is 1:2) into an esterification reaction kettle, heating the esterification reaction kettle to 60 ℃, and carrying out stirring reaction for 3 hours under normal pressure at the stirring speed of 1000 rpm. After the reaction, the reaction liquid is introduced into a decanter for standing and phase splitting, and the standing time is 3 hours. And respectively introducing an upper layer liquid (ester phase) and a lower layer liquid (water phase) obtained after phase separation in a decanter into a rinsing bath and a flash tank, and then purifying the product ester and recovering raw materials (mainly eutectic solvent, carboxylic acid and alcohol). Wherein the operation pressure of the rinsing bath is normal pressure, the operation temperature is room temperature, a product methyl decanoate with the mass fraction of 94 percent, namely high-purity ester, is extracted from the top of the rinsing bath, and a mixture of a eutectic solvent and water is extracted from the bottom and introduced into a flash tank; the operating pressure of the flash tank is 0.001bar, the operating temperature is 150 ℃, unreacted raw materials and a mixture containing water and ester are extracted from the top of the flash tank, and a eutectic solvent with the mass fraction of 99.99% is extracted from the bottom of the flash tank. The eutectic solvent obtained at the bottom of the flash tank is respectively returned to the esterification reaction kettle for cyclic utilization after heat exchange of a heat exchanger to 60 ℃. Introducing the mixture extracted from the top of the flash tank into an alcohol recovery tower, wherein the actual tower plate number of the alcohol recovery tower is 35, the operating pressure is normal pressure, the operating reflux ratio is 5.5, unreacted alcohol is obtained at the top of the alcohol recovery tower, and the unreacted alcohol is cooled to 60 ℃ by a heat exchanger and then returns to the esterification reaction kettle for recycling. Introducing the material in the tower kettle of the alcohol recovery tower into a carboxylic acid recovery tower, wherein the actual tower plate number of the carboxylic acid recovery tower is 42, the operating pressure is normal pressure, the operating reflux ratio is 4.5, obtaining byproduct water at the tower top of the acid recovery tower, finally removing water from an esterification reaction system, obtaining a mixed material containing unreacted carboxylic acid and partial product in the tower kettle of the acid recovery tower, cooling to 60 ℃ by a heat exchanger, and returning to the esterification reaction kettle for recycling. The yield of methyl decanoate in example 15 was 99.5% with a purity of 94%.
Example 16
The following treatment is carried out according to the flow of fig. 2:
adding 2.5mol of dodecanoic acid, 3.125mol of ethanol and 3.75mol of trimethyl cyclohexyl ammonium methanesulfonate-p-toluenesulfonic acid eutectic solvent (the molar ratio of trimethyl cyclohexyl ammonium methanesulfonate to p-toluenesulfonic acid is 1:2) into an esterification reaction kettle, heating the esterification reaction kettle to 60 ℃, and stirring and reacting for 3 hours under normal pressure at the stirring speed of 1000 rpm. After the reaction, the reaction liquid is introduced into a decanter for standing and phase splitting, and the standing time is 3 hours. And respectively introducing an upper layer liquid (ester phase) and a lower layer liquid (water phase) obtained after phase separation in a decanter into a rinsing bath and a flash tank, and then purifying the product ester and recovering raw materials (mainly eutectic solvent, carboxylic acid and alcohol). Wherein the operation pressure of the rinsing bath is normal pressure, the operation temperature is room temperature, the product ethyl dodecanoate with the mass fraction of 91 percent, namely high-purity ester, is extracted from the top of the rinsing bath, and the mixture of the eutectic solvent and water is extracted from the bottom and introduced into a flash tank; the operating pressure of the flash tank is 0.001bar, the operating temperature is 125 ℃, unreacted raw materials and a mixture containing water and ester are extracted from the top of the flash tank, and a eutectic solvent with the mass fraction of 99.99% is extracted from the bottom of the flash tank. The eutectic solvent obtained at the bottom of the flash tank is respectively returned to the esterification reaction kettle for cyclic utilization after heat exchange of a heat exchanger to 60 ℃. Introducing the mixture extracted from the top of the flash tank into an alcohol recovery tower, wherein the actual tower plate number of the alcohol recovery tower is 40, the operating pressure is normal pressure, the operating reflux ratio is 5.7, and unreacted alcohol is obtained at the top of the alcohol recovery tower, is cooled to 60 ℃ by a heat exchanger and then returns to the esterification reaction kettle for recycling. Introducing the material in the tower kettle of the alcohol recovery tower into a carboxylic acid recovery tower, wherein the actual tower plate number of the carboxylic acid recovery tower is 45, the operating pressure is normal pressure, the operating reflux ratio is 3.8, obtaining byproduct water at the top of the acid recovery tower, finally removing water from an esterification reaction system, obtaining a mixed material containing unreacted carboxylic acid and partial product in the tower kettle of the acid recovery tower, cooling to 60 ℃ by a heat exchanger, and returning to the esterification reaction kettle for recycling. The yield of ethyl dodecanoate was 99.3% and the purity was 91% in example 16.
Example 17
The following treatment is carried out according to the flow of fig. 2:
adding 2.5mol of myristic acid, 2.5mol of ethanol and 0.75mol of trimethyl cyclohexyl ammonium methanesulfonate-p-toluenesulfonic acid eutectic solvent (the molar ratio of trimethyl cyclohexyl ammonium methanesulfonate to p-toluenesulfonic acid is 1:2) into an esterification reaction kettle, heating the esterification reaction kettle to 60 ℃, and carrying out stirring reaction for 4 hours under normal pressure at the stirring speed of 1000 rpm. After the reaction, the reaction liquid is introduced into a decanter for standing and phase splitting, and the standing time is 4 hours. And respectively introducing an upper layer liquid (ester phase) and a lower layer liquid (water phase) obtained after phase separation in a decanter into a rinsing bath and a flash tank, and then purifying the product ester and recovering raw materials (mainly eutectic solvent, carboxylic acid and alcohol). Wherein the operation pressure of the rinsing bath is normal pressure, the operation temperature is room temperature, the product ethyl myristate with the mass fraction of 92 percent, namely high-purity ester, is extracted from the top of the rinsing bath, and the mixture of the eutectic solvent and water is extracted from the bottom and introduced into a flash tank; the operating pressure of the flash tank is 0.02bar, the operating temperature is 210 ℃, unreacted raw materials and a mixture containing water and ester are extracted from the top of the flash tank, and a eutectic solvent with the mass fraction of 99.99% is extracted from the bottom of the flash tank. The eutectic solvent obtained at the bottom of the flash tank is respectively returned to the esterification reaction kettle for cyclic utilization after heat exchange of a heat exchanger to 60 ℃. Introducing the mixture extracted from the top of the flash tank into an alcohol recovery tower, wherein the actual tower plate number of the alcohol recovery tower is 45, the operating pressure is normal pressure, the operating reflux ratio is 5.5, unreacted alcohol is obtained at the top of the alcohol recovery tower, and the unreacted alcohol is cooled to 60 ℃ by a heat exchanger and then returns to the esterification reaction kettle for recycling. Introducing the material in the tower kettle of the alcohol recovery tower into a carboxylic acid recovery tower, wherein the actual tower plate number of the carboxylic acid recovery tower is 50, the operating pressure is normal pressure, the operating reflux ratio is 4, by-product water is obtained at the tower top of the acid recovery tower, finally water is removed from an esterification reaction system, the mixed material containing unreacted carboxylic acid and partial product is obtained in the tower kettle of the acid recovery tower, and the mixed material is cooled to 60 ℃ by a heat exchanger and then returned to the esterification reaction kettle for recycling. The yield of ethyl myristate in example 17 was 99.2% and the purity was 92%.
Example 18
The following treatment is carried out according to the flow of fig. 2:
adding 2.5mol of hexadecanoic acid, 2.5mol of ethanol and 0.75mol of octyl trimethyl ammonium methanesulfonate-p-toluenesulfonic acid eutectic solvent (the molar ratio of trimethyl cyclohexyl ammonium methanesulfonate to p-toluenesulfonic acid is 1:2) into an esterification reaction kettle, heating the esterification reaction kettle to 60 ℃, and stirring and reacting for 5 hours under normal pressure at the stirring speed of 1000 rpm. After the reaction, the reaction liquid is introduced into a decanter for standing and phase splitting, and the standing time is 5 hours. And respectively introducing an upper layer liquid (ester phase) and a lower layer liquid (water phase) obtained after phase separation in a decanter into a rinsing bath and a flash tank, and then purifying the product ester and recovering raw materials (mainly eutectic solvent, carboxylic acid and alcohol). Wherein the operation pressure of the rinsing bath is normal pressure, the operation temperature is room temperature, 93 percent of ethyl palmitate, namely high-purity ester, is extracted from the top of the rinsing bath, and a mixture of a eutectic solvent and water is extracted from the bottom and introduced into a flash tank; the operating pressure of the flash tank is 0.01bar, the operating temperature is 200 ℃, unreacted raw materials and a mixture containing water and ester are extracted from the top of the flash tank, and a eutectic solvent with the mass fraction of 99.99% is extracted from the bottom of the flash tank. The eutectic solvent obtained at the bottom of the flash tank is respectively returned to the esterification reaction kettle for cyclic utilization after heat exchange of a heat exchanger to 60 ℃. Introducing the mixture extracted from the top of the flash tank into an alcohol recovery tower, wherein the actual tower plate number of the alcohol recovery tower is 50, the operating pressure is normal pressure, the operating reflux ratio is 5.5, and unreacted alcohol is obtained at the top of the alcohol recovery tower and is cooled to 60 ℃ by a heat exchanger and then returns to the esterification reaction kettle for recycling. Introducing the material in the tower kettle of the alcohol recovery tower into a carboxylic acid recovery tower, wherein the actual tower plate number of the carboxylic acid recovery tower is 55, the operating pressure is normal pressure, the operating reflux ratio is 4.2, obtaining byproduct water at the tower top of the acid recovery tower, finally removing water from an esterification reaction system, obtaining a mixed material containing unreacted carboxylic acid and partial product in the tower kettle of the acid recovery tower, cooling to 60 ℃ by a heat exchanger, and returning to the esterification reaction kettle for recycling. The yield of ethyl palmitate in example 18 was 99.0% and the purity was 93%.
Example 19
The following treatment was carried out according to the flow of FIG. 1:
adding 2.5mol of octadecanoic acid, 2.5mol of ethanol and 0.75mol of octyl trimethyl ammonium methanesulfonate-p-toluenesulfonic acid eutectic solvent (the molar ratio of trimethyl cyclohexyl ammonium methanesulfonate to p-toluenesulfonic acid is 1:2) into an esterification reaction kettle, heating the esterification reaction kettle to 60 ℃, and carrying out stirring reaction for 6 hours under normal pressure at the stirring speed of 1000 rpm. After the reaction, the reaction liquid is introduced into a decanter for standing and phase splitting, and the standing time is 6 hours. And respectively introducing an upper layer liquid (ester phase) and a lower layer liquid (water phase) obtained after phase separation in a decanter into a rinsing bath and a flash tank, and then purifying the product ester and recovering raw materials (mainly eutectic solvent, carboxylic acid and alcohol). Wherein the operation pressure of the rinsing bath is normal pressure, the operation temperature is room temperature, 97% by mass of ethyl octadecanoate, namely high-purity ester, is extracted from the top of the rinsing bath, and the mixture of the eutectic solvent and water is extracted from the bottom and introduced into a flash tank; the operating pressure of the flash tank is 0.01bar, the operating temperature is 250 ℃, unreacted raw materials and a mixture containing water and ester are extracted from the top of the flash tank, and a eutectic solvent with the mass fraction of 99.99% is extracted from the bottom of the flash tank. The eutectic solvent obtained at the bottom of the flash tank is respectively returned to the esterification reaction kettle for cyclic utilization after heat exchange of a heat exchanger to 60 ℃. Introducing the mixture extracted from the top of the flash tank into an alcohol recovery tower, wherein the actual tower plate number of the alcohol recovery tower is 55, the operating pressure is normal pressure, the operating reflux ratio is 6, unreacted alcohol is obtained from the top of the alcohol recovery tower, and the unreacted alcohol is cooled to 60 ℃ by a heat exchanger and then returns to the esterification reaction kettle for recycling. Introducing the material in the tower kettle of the alcohol recovery tower into a carboxylic acid recovery tower, wherein the actual tower plate number of the carboxylic acid recovery tower is 60, the operating pressure is normal pressure, the operating reflux ratio is 3.6, obtaining byproduct water at the top of the acid recovery tower, finally removing water from an esterification reaction system, obtaining a mixed material containing unreacted carboxylic acid and partial product in the tower kettle of the acid recovery tower, cooling to 60 ℃ by a heat exchanger, and returning to the esterification reaction kettle for recycling. The yield of ethyl octadecanoate in example 19 was 98.7% and the purity was 97%.
As can be seen from the above examples, the yield and purity of the estolide prepared by the method provided by the invention are high, the yield of the prepared isobutyl isobutyrate is 98.7-99.8%, and the purity is 90.65-99%; the yield of butyl caproate is 98.9-99.5%, and the purity is 91.05-94.23%; the yield of the isoamyl hexanoate is 99.0 to 99.5 percent, and the purity is 90.82 to 96.61 percent; the yield of octyl octanoate is 99.1 percent, and the purity is 93 percent; the yield of the methyl decanoate is 99.5 percent, and the purity is 94 percent; the yield of the ethyl dodecanoate is 99.3 percent, and the purity is 91 percent; the yield of the ethyl myristate was 99.2%, and the purity was 92%; the yield of the ethyl palmitate is 99.0 percent, and the purity is 93 percent; the yield of ethyl octadecanoate is 98.7%, and the purity is 97%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (1)
1. A method for preparing a estolide, comprising the steps of:
carrying out vacuum drying pretreatment on imidazole and p-toluenesulfonic acid for 24 hours at 80 ℃, weighing the dried imidazole and p-toluenesulfonic acid according to the molar ratio of 1:2, placing the weighed imidazole and p-toluenesulfonic acid into a stirring reaction kettle, heating and stirring the imidazole and p-toluenesulfonic acid at 80 ℃ and the stirring speed of 800rpm for 30 minutes to form a colorless homogeneous liquid imidazole-p-toluenesulfonic acid eutectic solvent; adding 2.5mol of isobutyric acid, 2.5mol of isobutanol and 0.788mol of imidazole-p-toluenesulfonic acid eutectic solvent, wherein the molar ratio of imidazole to p-toluenesulfonic acid is 1:2, into an esterification reaction kettle, heating the esterification reaction kettle to 80 ℃, stirring and reacting for 3 hours under normal pressure, wherein the stirring speed is 1000rpm, introducing the reaction liquid into a decanter after the reaction, standing and phase-splitting, and standing for 3 hours; respectively introducing an upper liquid ester phase and a lower liquid water phase obtained after phase separation in a decanter into a flash tank 1 and a flash tank 2 for product ester purification and raw material recovery, wherein the upper liquid ester phase and the lower liquid water phase are mainly eutectic solvents, carboxylic acid and alcohol; wherein the operating pressure of the flash tank 1 is 0.01bar, the operating temperature is 90 ℃, a product isobutyl isobutyrate with the mass fraction of 91.37 percent, namely high-purity ester, is extracted from the top of the flash tank 1, and a eutectic solvent with the mass fraction of 99.99 percent is extracted from the bottom of the flash tank 1; the operating pressure of the flash tank 2 is 0.03bar, the operating temperature is 180 ℃, unreacted raw materials and a mixture containing water and ester are extracted from the top of the flash tank 2, and a eutectic solvent with the mass fraction of 99.99% is extracted from the bottom of the flash tank; the eutectic solvents obtained at the bottoms of the flash tanks 1 and 2 are respectively subjected to heat exchange by a heat exchanger to 80 ℃ and then returned to the esterification reaction kettle for cyclic utilization; introducing the mixture extracted from the top of the flash tank 2 into an alcohol recovery tower, wherein the actual tower plate number of the alcohol recovery tower is 22, the operating pressure is normal pressure, the operating reflux ratio is 4.8, unreacted alcohol is obtained at the tower top of the alcohol recovery tower, and the unreacted alcohol is cooled to 80 ℃ by a heat exchanger and then returns to an esterification reaction kettle for recycling; introducing the material in the tower kettle of the alcohol recovery tower into a carboxylic acid recovery tower, wherein the actual tower plate number of the carboxylic acid recovery tower is 28, the operating pressure is normal pressure, the operating reflux ratio is 2.4, by-product water is obtained at the tower top of the acid recovery tower, water is finally removed from an esterification reaction system, and the mixed material containing unreacted carboxylic acid and partial product is obtained in the tower kettle of the acid recovery tower, is cooled to 80 ℃ by a heat exchanger and then is returned to the esterification reaction kettle for recycling; or, imidazole and p-toluenesulfonic acid are subjected to vacuum drying pretreatment for 24 hours at 80 ℃, imidazole and p-toluenesulfonic acid are weighed according to the molar ratio of 1:2, the weighed imidazole and p-toluenesulfonic acid are placed in a stirring reaction kettle, the mixture is heated and stirred for 30 minutes at 80 ℃ and at the stirring speed of 800rpm to form colorless homogeneous liquid imidazole-p-toluenesulfonic acid eutectic solvent, 3mol of isobutyric acid, 2.5mol of isobutanol and 0.654mol of imidazole-p-toluenesulfonic acid eutectic solvent are added into the esterification reaction kettle, the esterification reaction kettle is heated to 80 ℃, the mixture is stirred and reacted for 3 hours at normal pressure, the stirring speed is 1000rpm, the reaction liquid is introduced into a decanter for standing and phase separation, the standing time is 3 hours, the upper layer liquid ester phase and the lower layer liquid aqueous phase obtained after phase separation in the decanter are respectively introduced into a flash tank 1 and a flash tank 2 for product ester purification and raw material recovery, the method mainly comprises eutectic solvent, carboxylic acid and alcohol, wherein the operating pressure of a flash tank 1 is 0.01bar, the operating temperature is 90 ℃, the product isobutyl isobutyrate with the mass fraction of 90.65 percent, namely high-purity ester, is extracted from the top of the flash tank 1, and the eutectic solvent with the mass fraction of 99.99 percent is extracted from the bottom; the operating pressure of the flash tank 2 is 0.01bar, the operating temperature is 150 ℃, unreacted raw materials and a mixture containing water and ester are extracted from the top of the flash tank 2, and a eutectic solvent with the mass fraction of 99.99% is extracted from the bottom of the flash tank; the eutectic solvents obtained at the bottoms of the flash tanks 1 and 2 are respectively subjected to heat exchange by a heat exchanger to 80 ℃ and then returned to the esterification reaction kettle for cyclic utilization; introducing the mixture extracted from the top of the flash tank 2 into an alcohol recovery tower, wherein the actual tower plate number of the alcohol recovery tower is 24, the operating pressure is normal pressure, the operating reflux ratio is 4.6, unreacted alcohol is obtained at the tower top of the alcohol recovery tower, and the unreacted alcohol is cooled to 80 ℃ by a heat exchanger and then returns to an esterification reaction kettle for recycling; introducing the material in the tower kettle of the alcohol recovery tower into a carboxylic acid recovery tower, wherein the actual tower plate number of the carboxylic acid recovery tower is 30, the operating pressure is normal pressure, the operating reflux ratio is 2.1, obtaining byproduct water at the tower top of the acid recovery tower, finally removing water from an esterification reaction system, obtaining a mixed material containing unreacted carboxylic acid and partial product in the tower kettle of the acid recovery tower, cooling to 80 ℃ by a heat exchanger, and returning to the esterification reaction kettle for recycling.
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| CN111039783A (en) * | 2019-12-21 | 2020-04-21 | 华东理工大学 | Method for synthesizing ethyl laurate by taking eutectic solvent based on benzyltrimethylammonium chloride as catalyst |
| CN111153794A (en) * | 2019-12-21 | 2020-05-15 | 华东理工大学 | Method for synthesizing ethyl palmitate by using dodecyl trimethyl ammonium chloride-based eutectic solvent catalyst |
| CN111138277A (en) * | 2019-12-21 | 2020-05-12 | 华东理工大学 | Method for synthesizing ethyl laurate by using eutectic solvent catalyst based on cetyl trimethyl ammonium bromide |
| CN111196793A (en) * | 2020-01-15 | 2020-05-26 | 北京化工大学 | Preparation method of 2, 5-furan dicarboxylic acid dialkyl ester |
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| CN112679354A (en) * | 2020-12-31 | 2021-04-20 | 浙江物美生物科技有限公司 | Production process of isopropyl myristate |
| CN112812008A (en) * | 2021-01-11 | 2021-05-18 | 大连理工大学 | Method for preparing diacid diester compound under catalysis of deep eutectic solvent |
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